US3966711A - 4-Alkyl-1,4-diaza-5-oxo-cycloheptanes and their 1-oxyls - Google Patents

4-Alkyl-1,4-diaza-5-oxo-cycloheptanes and their 1-oxyls Download PDF

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US3966711A
US3966711A US05/476,366 US47636674A US3966711A US 3966711 A US3966711 A US 3966711A US 47636674 A US47636674 A US 47636674A US 3966711 A US3966711 A US 3966711A
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Michael Rasberger
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Novartis Corp
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Ciba Geigy Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring

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  • the invention relates to new derivatives of 1,4-diaza-5-oxo-cycloheptane, a process for their manufacture, their use as light stabilizers for organic polymers and the polymers stabilised with these compounds.
  • R 1 , R 2 , R 3 and R 4 independently of one another each denote an alkyl group or R 1 and R 2 and/or R 3 and R 4 together with the C atom to which they are bonded form a cycloalkane ring
  • Y denotes hydrogen or the oxyl radical O.sup..
  • n denotes an integer from 1 to 4
  • X if n is 1, denotes an alkyl group which can be substituted by groups containing O, N or S, an alkenyl, alkinyl or aralkyl group or an aralkyl group substituted by hydroxyl or ester groups, if n is 2, an alkylene group which can be interrupted by O, NH or S or by groups containing O, N or S, or an alkenylene, alkinylene or bis(alkylene)arene group, if n is 3, a group ##EQU2## IN WHICH M RE
  • R 1 , R 2 , R 3 and R 4 denote an alkyl group, this can be, for example, methyl, ethyl, n-propyl, iso-propyl, tert.-butyl, n-amyl, sec.-amyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • R 1 and R 2 , or R 3 and R 4 together with C atom to which they are bonded form a cycloalkyl ring, this can be, for example, a cyclopentyl, cyclohexyl or cyclooctyl ring.
  • X denotes alkyl groups, these can be, for example, methyl, ethyl, propyl, iso-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl or n-octadecyl.
  • X is an alkyl group substituted by groups containing O, N or S
  • X can be, for example, the following groups: hydroxyalkyl such as --CH 2 CH 2 OH or --CH 2 CHOH--CH 3 ; carboxyalkyl such as --CH 2 COOH; alkyl substituted by ester groups, for example alkoxycarbonylalkyl such as --CH 2 COOCH 3 , --CH 2 COOC 2 H 5 , --CH 2 COOC 8 H 17 , --CH 2 COOC 12 H 25 or --CH 2 COOC 18 H 37 , or alkylcarbonyloxyalkyl such as --CH 2 CH 2 OOCCH 3 , --CH 2 CH 2 OOCC 7 H 15 , --CH 2 CH 2 OOCC 11 H 23 , --CH 2 CH 2 OOCC 17 H 35 or ##EQU4## or arylcarbonyloxyalkyl such as ##SPC1##
  • amidoalkyl such as alkylcarbonylaminoalkyl, for example --CH 2 CH 2 NHCOCH 3 , --CH 2 CH 2 NHCOC 17 H 35 or --CH 2 CH 2 CH 2 NHCOC 7 H 15 , or carbamoylalkyl such as --CH 2 CONH 2 or --CH 2 CH 2 CONH 2 , or alkylaminocarbonylalkyl such as --CH 2 CONHC 2 H 5 or --CH 2 CH 2 CONHC 12 H 25 , or arylaminocarbonyalkyl such as --CH 2 CH 2 CONHC 6 H 5 , or dialkylaminocarbonylalkyl such as --CH 2 CON(CH 3 ) 2 ; cyanoalkyl, for example --CH 2 CN or --CH 2 CH 2 CN; alkyl substituted by ether groups, such as alkoxy groups, for example --CH 2 OC 4 H 9 or --CH 2 CH 2 OC 8 H 17 ; alkyl substituted by thioether groups, such as alkyl
  • alkyl substituted by sulphoxide groups such as alkylsulphinylalkyl, for example --CH 2 CH 2 SOC 8 H 17
  • alkyl substituted by sulphone groups such as alkylsulphonylalkyl, for example --CH 2 CH 2 CH 2 SO 2 C 12 H 25
  • aminoalkyl such as aminoalkyl unsubstituted at the nitrogen atom, for example --CH 2 CH 2 NH 2 or --CH 2 CH 2 CH 2 NH 2 , or such as aminoalkyl substituted by alkyl at the nitrogen atom, for example --CH 2 CH 2 --N(CH 3 ) 2 , --CH 2 CH 2 CH 2 N(C 2 H 5 ) 2 or --CH 2 CH 2 NHCH 2 CH 2 CN.
  • X denotes alkenyl it can be, for example, propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, tetradecenyl or octadecenyl.
  • X denotes alkinyl, it can be, for example, propargyl.
  • X is unsubstituted aralkyl, it can be benzyl, ⁇ -phenylethyl or ⁇ , ⁇ -dimethylbenzyl.
  • X is an aralkyl radical substituted by hydroxyl or ester groups, it can be, for example, 3,5-di-tert.-butyl-4-hydroxybenzyl, 4-propionoxybenzyl or 4-ethoxycarbonylbenzyl.
  • alkylene radical is interrupted by O, NH or S or by groups containing O, N or S
  • it can be, for example, the following alkylene radicals: radicals interrupted by O or S, such as --(CH 2 ) 2 --O--(CH 2 ) 2 --, --(CH 2 ) 2 --S--(CH 2 ) 2 --, --CH 2 CH 2 S(CH 2 ) 2 SCH 2 CH 2 --, --CH 2 CH 2 S(CH 2 ) 3 SCH 2 CH 2 --, --CH 2 CH 2 S(CH 2 ) 4 SCH 2 CH 2 --, --CH 2 CH 2 S(CH 2 ) 8 SCH 2 CH 2 -- or --CH 2 CH 2 S(CH 2 ) 12 SCH 2 CH 2 --; radicals interrupted by NH or amino groups, such as ##EQU5## alkylene radicals interrupted by ester groups, such as ##EQU6## alkylene radicals interrupted by amide groups, such as --CH 2 CONH(CH 2 ) 2 NHCO--CH 2 --, --
  • radicals interrupted by sulphoxide groups such as --(CH 2 ) 2 --SO--(CH 2 ) 2 --, --CH 2 CH 2 --SO--CH 2 CH 2 --SO--CH 2 CH 2 --, --(CH 2 ) 2 --SO--(CH 2 ) 12 --SO--(CH 2 ) 2 -- or ##EQU7## radicals interrupted by sulphone groups such as CH 2 --CH 2 --SO 2 --CH 2 --CH 2 --, --CH 2 CH 2 --SO 2 --(CH 2 ) 6 --SO 2 --CH 2 CH 2 --, ##EQU8##
  • X denotes alkenylene or alkinylene, it can be, for example, 2-butenylene-1,4, 2-butinylene-1,4 or 2,4-hexadiinylene-1,6.
  • X denotes bis(alkylene)arene
  • it can be 1,2-bis-(methylene)-benzene, 1,3-bis-(methylene)-benzene, 1,4-bis-(methylene)-benzene, 1,2-bis-(ethylene)-benzene, 1,3-bis-(ethylene)-benzene, 1,4-bis-(ethylene)-benzene or 4,4'-bis-(methylene)-diphenyl.
  • the trivalent hydrocarbon radical T can be, for example, one of the following radicals: ##EQU9##
  • the tetravalent hydrocarbon radical Q can be, for example, the radical ##EQU10##
  • the salts of the compounds of the formula I with organic or inorganic acids can be, for example, salts of acetic acid, formic acid, tartaric acid, phenylphosphonic acid, maleic acid, phosphoric acid, hydrochloric acid, phosphorous acid or carbonic acid.
  • Preferred compounds of the formula I are those wherein R 1 , R 2 , R 3 and R 4 independently of one another denote alkyl with 1 to 8 C atoms or R 1 and R 2 and/or R 3 and R 4 together with the C atom to which they are bonded form a cyclopentyl or cyclohexyl ring, Y denotes --H or the oxyl radical --O.sup.., n denotes an integer from 1 to 4 and X, if n is 1, denotes alkyl with 1 to 20 C atoms which can be substituted by hydroxyl, carboxyl, ester, amide, nitrile, ether, thioether, sulphoxide, sulphone or amino groups, alkenyl or alkinyl with 3 to 18 C atoms or aralkyl with 7 to 15 C atoms, which can be substituted by hydroxyl or ester groups, if n is 2, alkylene with 1 to 12 C atoms,
  • R 1 , R 2 , R 3 and R 4 denote alkyl with 1 to 4 C atoms or R 1 and R 2 and R 3 and R 4 together with the C atom to which they are bonded form a cyclohexyl ring
  • Y denotes --H or the oxyl radical --O.sup..
  • Examples of specific compounds of the formula I are: 4-(2'-phenyl-2'-hydroxyethyl)-2,2,7,7-tetramethyl-1,4-diaza-5-oxo-cycloheptane, 4-(carboxymethyl)-2,2,7,7-tetramethyl-1,4-diaza-5-oxo-cycloheptane, 4-(octyloxycarbonylmethyl)-2,2,7,7-tetramethyl-1,4-diaza-5-oxo-cycloheptane, 4-(octadecyloxycarbonymethyl)-2,2,7,7-tetramethyl-1,4-diaza-5-oxo-cycloheptane, 4-(methoxycarbonylethyl)-2,2,7,7-tetramethyl-1,4-diaza-5-oxo-cycloheptane, 4-(ethoxycarbonylethyl)-2,2,7,7-tetramethyl-1,
  • the compounds according to the invention, of the formula I can be manufactured by reacting 5-oxo-1,4-diazacycloheptanes of the formula II ##EQU15## in which R 1 , R 2 , R 3 and R 4 independently of one another each denote an alkyl group or R 1 and R 2 and/or R 3 and R 4 together with the C atom to which they are bonded form a cycloalkane ring, with alkylating agents and optionally a) oxidising the compounds of the formula I, thus obtained, wherein Y is hydrogen, to compounds of the formula I in which Y represents the oxyl radical, or optionally b) converting compounds of the formula I thus obtained, wherein Y is hydrogen, into the corresponding salts by treatment with organic or inorganic acids.
  • the 5-oxo-1,4-diazacycloheptanes of the formula II used as the starting material are known substances which can be manufactured, for example, in accordance with the process described in Journal of Org. Chem. 14, 530 (1949), by reaction of the corresponding piperidones with hydrazoic acid or by Beckmann rearrangement of the piperidone-oximes.
  • Examples of such compounds of the formula II which are suitable for use as the starting material are: 2,2,7,7-tetramethyl-5-oxo-1,4-diazacycloheptane, 2,2,7,7-tetraisopropyl-5-oxo-1,4-diazacycloheptane, 2,7-dimethyl-2,7-diisopropyl-5-oxo-1,4-diazacycloheptane, 7,15-diaza-16-oxo-dispiro[5.1.5.4]heptadecane, 6,13-diaza-14-oxo-dispiro[4.1.4.4]pentadecane and 8,8-dimethyl-11-oxo-7,10-diazaspiro[5.6]dodecane.
  • the most versatile method is the reaction with organic halogen compounds of the formula X-Hal n , wherein Hal denotes chlorine, bromine or iodine and X and n have the abovementioned meaning, in the presence of molar amounts of a deprotonising agent, or after deprotonising the starting compound of the formula II with such a deprotonising agent.
  • a deprotonising agent or after deprotonising the starting compound of the formula II with such a deprotonising agent.
  • deprotonising agents but especially alkali metals, alkali metal hydrides, alkaline earth metal hydrides, alkali metal amides or alkali metal alcoholates.
  • organic halogen compounds X-Hal n which can be used according to the invention there may be mentioned: methyl iodide, ethyl bromide, n-propyl bromide, 1-n-dodecyl bromide, ethylene chlorohydrin, propionic acid chloroethyl ester, hexahydrobenzoic acid 2-chloroethyl ester, chloroacetic acid, sodium chloroacetate, ethyl chloroacetate, chloroacetamide, N-dimethylchloroacetamide, chloroacetanilide, chloroacetonitrile, 1- ⁇ -chloroethoxy-n-octane, 1- ⁇ -bromoethylmercaptobutane, allyl chloride, oleyl bromide, propargyl chloride, benzyl chloride, ⁇ -phenylethyl bromide, 3,5-di-tert.-butyl-4-
  • the reaction is preferably carried out in organic solvents such as, for example, in benzene, toluene, dimethylformamide, dimethylsulphoxide or their mixtures.
  • hydroxyalkylation of the diazacycloheptanones with formaldehyde gives hydroxymethyl compounds whilst with epoxides it gives 2-hydroxyalkyl compounds.
  • epoxides are ethylene oxide, propylene oxide or styrene oxide.
  • the reaction with formaldehyde is carried out in the presence of an alcohol, the corresponding alkoxymethyl derivatives are formed; for example, the N-butoxymethyl derivative is formed in the presence of butanol.
  • One method of alkylation for the introduction of aminoalkyl groups consists of the reaction of the diazacycloheptanones with formaldehyde and amines or their salts, preferably with secondary amines such as, for example, dimethylamine, diethylamine or their salts.
  • a further important method for the introduction of substituted alkyl groups is the base-catalysed addition of ⁇ , ⁇ -unsaturated carboxylic acid derivatives, above all of acrylonitrile, acrylic acid esters and acrylamide.
  • Vinylsulphones and vinylsulphoxides for example vinyl-benzylsulphone or divinylsulphone can also be added on under these conditions.
  • the 3-cyanoethyl derivatives can be converted into the 3-aminopropyl derivatives by hydrogenation.
  • the hydroxyalkyl compounds can be esterified to the acyloxyalkyl compounds with carboxylic acids.
  • Thioether compounds can be oxidised to the sulphoxides or the sulphones and ester compounds can be hydrolysed to the free carboxyl compounds.
  • the diazacycloheptanone derivatives according to the invention are basic compounds, they are able to form salts with organic or inorganic acids.
  • the salt formation takes place according to known methods by addition of the corresponding acid in stoichiometric amounts or in excess amounts, during or after the manufacture of the compounds of the formula I.
  • Acids which are suitable for this purpose are, for example, acetic acid, formic acid, tartaric acid, phenylphosphonic acid, maleic acid or phosphoric acid.
  • the light aging of organic polymers can on the one hand lead to degradation and deterioration of the mechanical properties, associated therewith, and, on the other hand, to a discolouration of the polymers. Both aging phenomena can also occur alongside one another.
  • the compounds according to the invention now protect organic polymers against both the adverse phenomena of light aging and, surprisingly, do so substantially more effectively than the known starting compounds of the formula II are able to do.
  • Polymers of which the light aging can be delayed or prevented by the compounds of the formula I according to the invention are, for example, the following categories which are industrially important.
  • Polymers which are derived from singly or doubly unsaturated hydrocarbons such as, for example, polyolefines such as polyethylene, which can optionally be crosslinked, polypropylene, polybutene-1, polyisobutene, polymethylbutene-1, polymethylpentene-1, polyisoprene, polybutadiene, polystyrene, copolymers of the monomers on which the homopolymers mentioned are based, such as ethylene-propylene copolymers, propylene-butene-1 copolymers, propylene-isobutene copolymers, styrene-butadiene copolymers and terpolymers of ethylene and propylene with a diene such as, for example, hexadiene, dicyclopentadiene or ethylidenenorbornene; mixtures of the abovementioned homopolymers such as, for example, mixtures of polypropylene and polyethylene, polypropy
  • Vinyl polymers containing halogen such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene and chlorinated rubbers.
  • Polymers which are derived from ⁇ , ⁇ -unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile, as well as their copolymers with other vinyl compounds, such as acrylonitrile/butadiene/styrene, acrylonitrile/styrene and acrylonitrile/styrene/acrylic ester copolymers.
  • Homopolymers and copolymers which are derived from epoxides such as polyethylene oxide or the polymers which are derived from bis-glycidyl ethers.
  • Polyacetals such as polyoxymethylene and polyoxyethylene, as well as polyoxymethylenes which contain ethylene oxide as a comonomer.
  • Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11 and polyamide 12.
  • Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene glycol terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate and their starting materials, such as lower terephthalic acid alkyl esters.
  • Crosslinked polymers which are derived from aldehydes, on the one hand, and phenols, ureas and melamines, on the other, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
  • Alkyd resins such as glycerine-phthalic acid resins and their mixtures with melamine-formaldehyde resins.
  • Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and vinyl compounds as crosslinking agents, and also their halogen-containing modifications of low flammability.
  • Natural polymers such as cellulose, rubber, proteins, and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methylcellulose.
  • Preferred polymers are polyethylene of high and low density, polypropylene, polybutadiene, polyvinyl chloride, polystyrene and its copolymers and mixtures thereof.
  • the new compounds are added to the substrates in a concentration of 0.01 to 5% by weight, calculated relative to the material to be stabilised.
  • 0.05 to 1.5, and especially preferentially 0.1 to 0.8, % by weight of the compounds, calculated relative to the material to be stabilised, are incorporated into the latter.
  • the incorporation can be effected after the polymerisation, for example by mixing the compounds and optionally further additives into the melt in accordance with the industrially customary methods, before or after shaping, or by applying the dissolved or dispersed compounds to the polymer, if necessary with subsequent evaporation of the solvent.
  • the new compounds can also be added to the polymers to be stabilised in the form of a master batch which contains these compounds, for example, in a concentration of 2.5 to 25% by weight.
  • crosslinked polyethylene the compounds are added before crosslinking.
  • Simple 2.6-dialkylphenols such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.
  • alkylated hydroquinones such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert,-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl)-phosphite, 3,5-di-tert.-butyl-4-hydroxyphenol-stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-adipate.
  • alkylated hydroquinones such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-di-tert.
  • Hydroxylated thiodiphenyl ethers such as, for example, 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)-disulphide.
  • Alkylidene-bisphenols such as, for example, 2,2'-methylene-bis-(6-tert.butyl-4-methylphenol),2,2'-methylene-bis-(6-tert.butyl-4-ethylphenol), 4,4'-methylene-bis-(6-tert.butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.butyl-phenol), 2,6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis
  • O-, N- and S-benzyl compounds such as, for example, 3,5,3',5'-tetra-tert.butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl ester, tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-amine and bis-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol terephthalate.
  • 3,5,3',5'-tetra-tert.butyl-4,4'-dihydroxydibenzyl ether 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl ester, tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-amine and bis-(4-tert.butyl-3-hydroxy-2,6-
  • 1.6 Hydroxybenzylated malonic esters such as, for example, 2,2-bis-3,5-di-tert.butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester, 2-(3-tert.butyl-4-hydroxy-5-methylbenzyl)-malonic acid dioctadecyl ester, 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-malonic acid di-dodecylmercapto ethylester and 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-malonic acid di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-ester.
  • 2,2-bis-3,5-di-tert.butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester 2-(3-tert.butyl-4-hydroxy-5-methylbenzyl
  • Hydroxybenzyl-aromatics such as, for example, 1,3,5-tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-di-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-phenol.
  • 1.8 s-Triazine compounds such as, for example, 2,4-bis-octylmercapto-6-(3,5-di-tert.butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5-tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate
  • esters of ⁇ -(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, etylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl-isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
  • monohydric or polyhydric alcohols such as, for example, methanol,
  • esters of ⁇ -(5-tert.butyl-4-hydroxy-3-methylphenylpropionic acid with monohydric or polyhydric alcohols such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethylisocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
  • monohydric or polyhydric alcohols such as, for example, methanol, ethanol, oct
  • esters of 3,5-ditert.butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethylisocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2]octane.
  • monohydric or polyhydric alcohols such as, for example, methanol, ethanol, octadecanol, 1,6
  • Benzylphosphonates such as, for example, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid diethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester and 5-tert.butyl-4-hydroxy-3-methylbenzyl-phosphonic acid dioctadecyl ester.
  • Aminoaryl derivatives such as, for example, phenyl-1-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, monooctyliminodibenzyl and dioctyliminodibenzyl and polymerised 2,2,4-trimethyl-1,2-dihydroquinoline.
  • 2-(2'-Hydroxyphenyl)-benztriazoles such as, for example, the 5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, 3'- ⁇ -methyl-benzyl-5'-methyl-, 3'- ⁇ -methylbenzyl-5'-methyl-5-chloro-, 4-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.amyl-, 3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'-di-tert.amyl- derivative
  • 2-Hydroxy-benzophenones such as, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxyderivative.
  • 1,3-Bis-(2'-hydroxy-benzoyl)-benzenes such as, for example, 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'octyloxy-benzoyl)-benzene and 1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.
  • Esters of optionally substituted benzoic acids such as, for example, phenyl salicylate, octylphenyl salicylate, di-benzoylresorcinol, bis-(4-tert.butylbenzoyl)-resorcinol, benzoylresorcinol and 3,5-di-tert.butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl ester, octadecyl ester or 2-methyl-4,6-di-tert.butyl-phenyl ester.
  • benzoic acids such as, for example, phenyl salicylate, octylphenyl salicylate, di-benzoylresorcinol, bis-(4-tert.butylbenzoyl)-resorcinol, benzoylresorcinol and 3,5-di-tert.butyl-4-hydroxybenzoic acid 2,4-d
  • Acrylates such as, for example, ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ -carbomethoxy-cinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamic acid methyl ester or butyl ester and N-( ⁇ -carbomethoxy-vinyl)-2-methyl-indoline.
  • Nickel compounds such as, for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel complexes of bis-[2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such as the 2:1 complex, optionally with additional ligands such as 2-ethyl-caproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.butylbenzyl-phosphonic acid monoalkyl esters, such as the methyl, ethyl or butyl ester, the nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl-undecylketonoxime and nickel 3,5-d
  • Sterically hindered amines such as, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-tetramethylpiperidyl)-sebacate, and 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decane-2,4-dione.
  • 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-tetramethylpiperidyl)-sebacate
  • 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decane-2,4-dione 3-n-octyl-7,7,9,9-tetramethyl-1
  • Oxalic acid diamides such as, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert. butyl-oxanilide, mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxydisubstituted oxanilides.
  • Metal deactivators such as, for example, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyloyloxalic acid dihydrazide, N,N'-bis-salicyloyl-hydrazine and N,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)hydrazine.
  • oxanilide isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyloyloxalic acid
  • Phosphites such as, for example, triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tri-(nonylphenyl)-phosphite, trilaurylphosphite, trioctadecylphosphite, 3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl)-phosphite.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myrystyl or tridecyl esters, salts of 2-mercaptobenzimidazole, for example the Zn salt, and diphenylthiourea.
  • Polyamide stabilisers such as, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilisers such as, for example, melamine, benzoguanamine, polyvinylpyrrolidone, dicyandiamide, triallyl-cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, and alkali metal salts and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate or K palmitate.
  • PVC stabilisers such as, for example, organic tin compounds, organic lead compounds and barium-cadmium salts of fatty acids.
  • Nucleating agents such as for example 4-tert.butylbenzoic acid, adipic acid and diphenylacetic acid.
  • additives such as, for example, plasticisers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, pigments, optical brighteners, flameproofing agents and antistatic agents.
  • Example 2 The procedure is as in Example 1 except that, instead of the n-octyl bromide used in that example, 0.1 mol in each case of the alkylating agents given in column 1 of Table 1 is employed and the products listed in column 2 are obtained.
  • a part of the pressed blank obtained is cut out and pressed between two high gloss hard aluminium foils for 6 minutes at 260°C and 12 tons pressure, using a manual hydraulic laboratory press, to give an 0.5 mm thick film which is immediately chilled in cold water.
  • the 0.1 mm thick test film is produced from this 0.5 mm thick film under exactly the same conditions.
  • Pieces of 60 ⁇ 44 mm are now punched from the 0.1 mm thick film and exposed in the Xenotest 150.
  • these test specimens are taken from the light exposure apparatus and examined for their carbonyl content in an IR-spectrophotometer. The increase in the carbonyl extinction during exposure to light is a measure of the photo-oxidative degradation of the polymers [see L.

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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
US05/476,366 1973-06-22 1974-06-05 4-Alkyl-1,4-diaza-5-oxo-cycloheptanes and their 1-oxyls Expired - Lifetime US3966711A (en)

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Cited By (24)

* Cited by examiner, † Cited by third party
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US4190571A (en) * 1977-09-21 1980-02-26 The B. F. Goodrich Company Substituted 2-keto-1,4-diazacycloalkanes and UV-light-stabilized compositions containing them
US4207228A (en) * 1977-09-21 1980-06-10 The B. F. Goodrich Company UV-Light-stabilized compositions containing substituted 1,5-diazacycloalkanes, novel compounds and synthesis thereof
US4362831A (en) * 1978-12-08 1982-12-07 Adeka Argus Chemical Co., Ltd. Synergistic light and heat stabilizer compositions for synthetic resins and resin compositions containing the same
US4670131A (en) * 1986-01-13 1987-06-02 Exxon Chemical Patents Inc. Method for controlling fouling of hydrocarbon compositions containing olefinic compounds
US4814443A (en) * 1987-08-13 1989-03-21 The Dow Chemical Company Preparation of hydroxyalkylpiperazinones by reacting glyoxal with hydroxyalkyldiamines
EP0361536A1 (en) 1985-07-22 1990-04-04 The B.F. Goodrich Company Process for preparing polysubstituted piperazinones
US5098681A (en) * 1990-08-16 1992-03-24 The Dow Chemical Company Process for absorption of sulfur compounds from fluids
US5342593A (en) * 1990-08-16 1994-08-30 The Dow Chemical Company Process for absorption of sulfur compounds from fluids
US5346545A (en) * 1992-03-05 1994-09-13 Ciba-Geigy Corporation Stabilization
US5378276A (en) * 1993-02-23 1995-01-03 Ciba-Geigy Corporation Diketopyrrolopyrroles containing nitroxyl groups
US5389141A (en) * 1992-03-05 1995-02-14 Ciba-Geigy Corporation Stabilization of pyrrolopyrrole pigments
EP0638616A1 (de) * 1993-08-13 1995-02-15 Ciba-Geigy Ag Pigmentsalze
US6300533B1 (en) 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
US6344560B1 (en) 2000-05-03 2002-02-05 Uniroyal Chemical Company, Inc. Nitroaromatic solubilizer for nitroxyls in aromatic solvents
US6403850B1 (en) 2000-01-18 2002-06-11 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6653414B2 (en) 1999-12-02 2003-11-25 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6660181B2 (en) 1999-12-02 2003-12-09 Crompton Corporation Inhibition of polymerization of unsaturated monomers
US20040010159A1 (en) * 2000-10-16 2004-01-15 Brigitte Benage Blends of quinone alkide and nitroxyl compounds and polymerization inhibitors
US6685823B2 (en) 2000-10-16 2004-02-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US6767949B1 (en) 1999-11-25 2004-07-27 Ciba Specialty Chemicals Corporation Composition and method for color improvement of nitroxyl containing polymers
US20050113626A1 (en) * 1999-12-03 2005-05-26 Uniroyal Chemical Company, Inc., A Corporation Of The State Of Delaware Composition and method for inhibiting polymerization and polymer growth
US20060069218A1 (en) * 2004-09-28 2006-03-30 Vilan Kosover Sulfonated nitrophenols as polymerization inhibitors
US20060122341A1 (en) * 2004-12-03 2006-06-08 Vilan Kosover Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors
US20070256352A1 (en) * 2006-05-03 2007-11-08 Wood Mervin G Substituted hexahydro-1,4-diazepin-5-ones and compositions stabilized therewith

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3040029A (en) * 1962-06-19 Preparation of homopiperazine and al-

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1336682A (en) * 1971-01-26 1973-11-07 Ciba Geigy Uk Ltd Chemical compositions optical system for orthogonalizing image field of projection

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3040029A (en) * 1962-06-19 Preparation of homopiperazine and al-

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190571A (en) * 1977-09-21 1980-02-26 The B. F. Goodrich Company Substituted 2-keto-1,4-diazacycloalkanes and UV-light-stabilized compositions containing them
US4207228A (en) * 1977-09-21 1980-06-10 The B. F. Goodrich Company UV-Light-stabilized compositions containing substituted 1,5-diazacycloalkanes, novel compounds and synthesis thereof
US4362831A (en) * 1978-12-08 1982-12-07 Adeka Argus Chemical Co., Ltd. Synergistic light and heat stabilizer compositions for synthetic resins and resin compositions containing the same
EP0361536A1 (en) 1985-07-22 1990-04-04 The B.F. Goodrich Company Process for preparing polysubstituted piperazinones
US4670131A (en) * 1986-01-13 1987-06-02 Exxon Chemical Patents Inc. Method for controlling fouling of hydrocarbon compositions containing olefinic compounds
US4814443A (en) * 1987-08-13 1989-03-21 The Dow Chemical Company Preparation of hydroxyalkylpiperazinones by reacting glyoxal with hydroxyalkyldiamines
US5098681A (en) * 1990-08-16 1992-03-24 The Dow Chemical Company Process for absorption of sulfur compounds from fluids
US5342593A (en) * 1990-08-16 1994-08-30 The Dow Chemical Company Process for absorption of sulfur compounds from fluids
US5346545A (en) * 1992-03-05 1994-09-13 Ciba-Geigy Corporation Stabilization
US5389141A (en) * 1992-03-05 1995-02-14 Ciba-Geigy Corporation Stabilization of pyrrolopyrrole pigments
US5378276A (en) * 1993-02-23 1995-01-03 Ciba-Geigy Corporation Diketopyrrolopyrroles containing nitroxyl groups
EP0638616A1 (de) * 1993-08-13 1995-02-15 Ciba-Geigy Ag Pigmentsalze
US6300533B1 (en) 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
EP1232212B1 (en) * 1999-11-25 2006-05-10 Ciba SC Holding AG Composition and method for color improvement of nitroxyl containing polymers
US6767949B1 (en) 1999-11-25 2004-07-27 Ciba Specialty Chemicals Corporation Composition and method for color improvement of nitroxyl containing polymers
AU775926B2 (en) * 1999-11-25 2004-08-19 Ciba Specialty Chemicals Holding Inc. Composition and method for color improvement of nitroxyl containing polymers
US6653414B2 (en) 1999-12-02 2003-11-25 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6660181B2 (en) 1999-12-02 2003-12-09 Crompton Corporation Inhibition of polymerization of unsaturated monomers
US20050113626A1 (en) * 1999-12-03 2005-05-26 Uniroyal Chemical Company, Inc., A Corporation Of The State Of Delaware Composition and method for inhibiting polymerization and polymer growth
US7943809B2 (en) 1999-12-03 2011-05-17 Chemtura Corporation Composition and method for inhibiting polymerization and polymer growth
US20100093897A1 (en) * 1999-12-03 2010-04-15 Chemtura Corporation Composition and method for inhibiting polymerization and polymer growth
US20050113625A1 (en) * 1999-12-03 2005-05-26 Uniroyal Chemical Company, Inc. Composition and method for inhibiting polymerization and polymer growth
US6403850B1 (en) 2000-01-18 2002-06-11 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6344560B1 (en) 2000-05-03 2002-02-05 Uniroyal Chemical Company, Inc. Nitroaromatic solubilizer for nitroxyls in aromatic solvents
US7473795B2 (en) 2000-10-16 2009-01-06 Uniroyal Chemical Company, Inc. Blends of quinone alkide and nitroxyl compounds as polymerization inhibitors
US20060155140A1 (en) * 2000-10-16 2006-07-13 Uniroyal Chemical Company, Inc A Corporation Of The State Of Delaware Blends of quinone alkide and nitroxyl compounds as polymerization inhibitors
US6899806B2 (en) 2000-10-16 2005-05-31 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US6902663B2 (en) 2000-10-16 2005-06-07 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US20040010159A1 (en) * 2000-10-16 2004-01-15 Brigitte Benage Blends of quinone alkide and nitroxyl compounds and polymerization inhibitors
US7022220B2 (en) 2000-10-16 2006-04-04 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US20040104146A1 (en) * 2000-10-16 2004-06-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US7045647B2 (en) 2000-10-16 2006-05-16 Uniroyal Chemical Company, Inc. Blends of quinone alkide and nitroxyl compounds and polymerization inhibitors
US6685823B2 (en) 2000-10-16 2004-02-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US20040106753A1 (en) * 2000-10-16 2004-06-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US20040089586A1 (en) * 2000-10-16 2004-05-13 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US7691952B2 (en) 2004-09-28 2010-04-06 Chemtura Corporation Sulfonated nitrophenols as polymerization inhibitors
US20060069218A1 (en) * 2004-09-28 2006-03-30 Vilan Kosover Sulfonated nitrophenols as polymerization inhibitors
US7696290B2 (en) 2004-12-03 2010-04-13 Crompton Corporation Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors
US20060122341A1 (en) * 2004-12-03 2006-06-08 Vilan Kosover Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors
US20100127218A1 (en) * 2004-12-03 2010-05-27 Chemtura Corporation Aromatic sulfonic acids, amines and nitrophenols in combination with nitroxyl radical-containing compounds or c-nitrosoanilines as polymerization inhibitors
US7728083B1 (en) 2004-12-03 2010-06-01 Chemtura Corporation Aromatic sulfonic acids, amines and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosoanilines as polymerization inhibitors
US20070256352A1 (en) * 2006-05-03 2007-11-08 Wood Mervin G Substituted hexahydro-1,4-diazepin-5-ones and compositions stabilized therewith

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IE39302L (en) 1974-12-22
FR2234297B1 (enrdf_load_stackoverflow) 1978-01-13
GB1453985A (en) 1976-10-27
IE39302B1 (en) 1978-09-13
NL7408297A (enrdf_load_stackoverflow) 1974-12-24
CH579118A5 (enrdf_load_stackoverflow) 1976-08-31
DE2428877A1 (de) 1975-01-23
DK336674A (enrdf_load_stackoverflow) 1975-04-21
BE816696A (fr) 1974-12-23
LU70362A1 (enrdf_load_stackoverflow) 1976-05-31
JPS5088143A (enrdf_load_stackoverflow) 1975-07-15
FR2234297A1 (enrdf_load_stackoverflow) 1975-01-17

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